The Emmy-nominated talkshow, hosted by Neil deGrasse Tyson, will return in October, reported Entertainment Weekly.
"I couldn't think of a more appropriate guest to kick off our second season. President Bill Clinton is a public figure whose impact and influence spans politics, pop culture and science-with an occasional dose of humor.
"That's exactly the mission statement for 'StarTalk', and I look forward to sharing our conversation with viewers," Tyson said.
"Dead Man Walking" actress Susan Sarandon, comedian Larry Wilmore and magicians Penn and Teller will also appear during season two of the science-themed late-night talkshow.